Polymer 46 (2005) 5396–5405

www.elsevier.com/locate/polymer

Synthesis and characterization of diblock copolymers based on

crystallizable poly(3-caprolactone) and mesogen-jacketed liquid
crystalline polymer block
Yong-Feng Zhao, Xinghe Fan*, Xiaofang Chen, Xinhua Wan, Qi-Feng Zhou*
Department of Polymer Science and Engineering, College of Chemistry and Molecular Engineering, Peking University, Beijing 100871, China
Received 14 January 2005; received in revised form 14 March 2005; accepted 15 March 2005
Available online 22 April 2005

Abstract
Diblock copolymers comprising crystallizable poly(3-caprolactone) and poly{2,5-bis[(4-methoxyphenyl)oxycarbonyl]styrene} (PMPCS)
were synthesized by ring-opening polymerization of 3-caprolactone and subsequent atom transfer radical polymerization (ATRP) of MPCS.
The molecular structure of the copolymers was confirmed by 1H NMR spectroscopy and GPC. Kinetic study of ATRP showed that the
polymerization proceeded in a controlled way up to high conversions. Three series of diblock copolymers were obtained with relatively
narrow polydispersity indices (PDI%1.11) and PCL blocks of 8000, 12,900, and 22,800 molecular weights, respectively. The existence of
microphase separation was identified by differential scanning calorimetry (DSC) and directly observed through transmission electron
microscopy (TEM). The melting behavior of PCL block was significantly affected by the length of PCL block and composition of PMPCS.
The thermotropic liquid crystalline behavior was examined by polarized optical microscopy (POM) and DSC. The result showed that the
diblock copolymer exhibited liquid crystalline behavior when the degree of polymerization (DP) of PMPCS block was not less than 44.
q 2005 Elsevier Ltd. All rights reserved.

Keywords: Liquid crystalline block copolymer; Crystalline block copolymer; Microphase separation

1. Introduction competition between crystallization and microphase separ-

The self-assembly behavior of block copolymers has
been extensively studied due to their abilities to self-
organize into various phase morphologies, such as lamellae,
double gryroid, cylinders, and spheres in bulk depending on
the volume fraction of the block chains and the separation
power denoted by cN (cZFlory–Huggins interaction
parameter, NZtotal chain length) [1,2]. If one or more of
the blocks are crystallizable, the microphase separation
behavior becomes more complicated [3–6]. The final
morphology of the block copolymer is determined by the
crystallization temperature of the crystallizable block (Tc),
the glass transition temperature of the amorphous block (Tg)
and the order–disorder temperature (ODT). Because the
* Corresponding authors. Tel.: C86 106 277 2417; fax: C86 106 275
1708.
E-mail addresses: fanxh@chem.pku.edu.cn (X. Fan),
qfzhou@pku.edu.cn (Q.-F. Zhou).
0032-3861/$ - see front matter q 2005 Elsevier Ltd. All rights reserved.
doi:10.1016/j.polymer.2005.03.095
ation has important effect on the final morphology of the
crystallizable block copolymers, extensive studies have
been carried out to understand the effects of crystallization
on the microphase separated morphology, as well as the
effects of the microphase separation on the crystallization
[7–13].
In recent years, many research groups have focused their
interests on the synthesis and characterization of liquid
crystalline (LC)-isotropic (I) block copolymers [14–18].
Because special functions can be introduced via the LC
segment into the micro- or nanostructure of the block
copolymers, these block copolymers are candidates for the
development of new functional materials. The delicate
competition between the liquid crystalline phase and
microphase separated morphology is still under investi-
gation by many scientists [16,18–21]. Considering the
special effects of crystallizable segment and liquid crystal-
line segment on block copolymers, it is reasonable to
suppose that diblock copolymer, which combine the
crystalline segment and liquid crystalline segment, is
greatly interesting because this kind of block copolymer
 Y.-F. Zhao et al. / Polymer 46 (2005) 5396–5405 5397

may offer opportunities to modify the microphase separated investigated depending on the composition of block
structures and morphology through both crystallizable block copolymers. The microphase separations of block copoly-
and liquid crystalline block. As a result, the structure of mers are also demonstrated by DSC and TEM.
‘order-within-order’ would be generated. As we know,
microphase separation of the diblock copolymers usually
occurs on a scale of 10–100 nm, low ordered liquid
crystalline phase formed by the liquid crystalline blocks is 2. Experimental section
usually on a scale of a few nanometer, and crystallization of
the crystalline blocks is on an atomic packing scheme of a 2.1. Materials
few tenths of nanometer [12,21].
In the present study, we are specifically interested in the Toluene was dried by refluxing over Na metal and
synthesis of series of crystalline–liquid crystalline diblock distilled under N2 atmosphere just before use. 3-Caprolac-
copolymers which based on crystallizable poly(3-caprolac- tone (CL) (99%, from Acros) was dried over calcium
tone) and mesogen-jacketed liquid crystalline polymers hydride at room temperature and distilled under reduced
(MJLCPs). Different from the conventional side chain liquid pressure. Aluminum iso-propoxide (Al(OiPr)3) was purified
crystalline polymers (SCLCPs) with long spacers, MJLCPs by distilling under reduced pressure. Chlorobenzene was
have no spacers between the backbones and mesogenic side purified by washing with concentrated sulphuric acid to
chains. The spatial requirement of the bulky side chains remove thiophene, followed by washing with water, being
leads to the extended and stiffened conformation of the dried with anhydrous calcium chloride and being distilled.
backbones [22]. MJLCPs have unique properties different Cuprous bromide (CuBr) was synthesized from CuBr2 and
from the common SCLCPs such as stable nematic phase in a purified by stirring in acetic acid, washing with methanol
broad temperature range and stiff chains by strongly and then dried in vacuum just before use. N,N,N 0 ,N 00 ,N 00 -
coupling of backbone and side chains [22,23]. The first Pentamethyldiethylenetriamine (PMDETA) (99.5%, from
MJLCP based diblock copolymer, poly(styrene-block-2,5-bis TCI) and 2-bromo-2-methylpropionyl bromide (98%, from
[(4-methoxyphenyl)oxycarbonyl]styrene) (PS-b-PMPCS), Acros) were used as obtained without further purification.
was successfully prepared via 2,2,6,6-tertramethyl-1-piper- MPCS was synthesized according to the literature [37].
idinyloxy (TEMP) mediated living-free radical polymeriz-
ation [24]. The temperature-induced self-assemble behavior
2.2. Preparation of poly(3-caprolactone) (PCL)
of this novel diblock copolymer was examined in p-xylene
[25]. Meanwhile, the bulk phase behavior shows hierarch-
The synthetic procedures were listed in Schemes 1 and 2.
ical assembly structure [26]. The PMPCS rigid column is
Previously, glass reactor with a magnetic bar and rubber cap
formed due to the strong interaction between the side-chain
was flamed and purged nitrogen for three times. Toluene
mesogens and polymer backbone. The macromolecular
and CL were introduced into the reactor with a syringe.
columns possess orientational order, and parallel to the
Then the initiator solution was added with a syringe. CL was
lamellar normal. Recently, we reported the preparation of
polymerized at 0 8C under N2 atmosphere. The reaction was
PMPCS via ATRP in anisole [27]. It provided a new way to
stopped by adding an excess (relative to initiator) 2 N HCl
synthesize block copolymers from macro-initiators.
solution. The reaction solution was washed with water to
Copolymers containing poly(3-caprolactone) (PCL) are
neutral pH and the polymer was recovered by precipitation
especially interesting because they are miscible with a wide
range of polymers, and they have features like crystal-
lizability, lack of toxicity, ability to disperse pigments,
low-temperature adhesiveness, and printability [28,29].
Different types of block copolymers that include amor-
phous–crystalline copolymers and double crystalline copo-
lymers with PCL as crystalline block have been studied
thoroughly [28,30–34]. In addition, PCL is one of
biodegradable polymers which have been used to prepare
functional materials [35,36]. The degradability of PCL may
be used to investigate the morphology of block copolymer
and may result in interesting materials.
The purpose of this paper is to synthesize three series of
well-defined diblock copolymer, PCL-b-PMPCS, consist of
different length of crystallizable segment PCL and liquid
crystalline segment PMPCS by the ROP of 3-CL and
subsequent ATRP of MPCS. Thermal properties and liquid
crystalline behaviors of the diblock polymers have been Scheme 1. Synthesis of the PCL macroinitiators.
5398 Y.-F. Zhao et al. / Polymer 46 (2005) 5396–5405
Scheme 2. Synthesis of PCL-b-PMPCS diblock copolymers by ATRP.
in petrol ether. The polymer was dried under reduced
pressure at room temperature until constant weight.
2.3. Fraction of PCL
To obtain relatively low polydispersity sample, PCL was
fractioned by dropping petrol ether to THF solution of PCL
slowly.
2.4. Preparation of PCL-Br
PCL was dissolved in dry THF, and 5-fold excess
triethylamine (NEt3) (relative to OH groups), 5-fold excess
2-bromo-2-methylpropionyl bromide was dropped slowly
under ice bath. After the reaction solution stirred for two
days at room temperature, the solution was filtrated to
remove NEt3HCl. The solution was evaporated and the
product was dissolved in CH2Cl2, washed with 5% NaHCO3
solution and water, respectively, dried over anhydrous
Na2SO4, rotary evaporated most of the solvent and poured
into methanol. The crude PCL-Br macroinitiator was re-
precipitated in methanol several times and dried in vacuum.
2.5. Preparation of PCL-b-PMPCS
PCL-b-PMPCS diblock copolymer was synthesized by
atom transfer radical polymerization in chlorobenzene. A
tube was charged with MPCS, PCL-Br, CuBr, PMDETA
(n/1/1/1) (in molar ratios) and chlorobenzene, then sealed
after degassed in vacuum and flushed with N2 for three
times. Polymerization was carried out at 90 8C. Diluted with
tetrahydrofuran (THF), the reaction solution was filtered
over neutral aluminum oxide to remove catalyst complex,
precipitated in methanol and dried in vacuum. The
conversion of polymerization was determined gravimetri-
cally. The samples are abbreviated as ‘PCLxPMPCSy’
where x and y represents the DP of PCL and PMPCS,
respectively, calculated from the 1H NMR spectra.
2.6. Measurements
Gel permeation chromatography (GPC) measurements
were carried out in THF on a Waters 2410 instrument
equipped with three Waters m-Styragel columns (103, 104,
and 105 Å) at 35 8C, with a Waters 2410 RI detector.
Calibration was based on low polydispersity polystyrene
standards. The number-averaged molecular weight (Mn) of
PCL was calibrated by reference to a universal calibration
curve and polystyrene standards in THF at 35 8C (KPSZ
1.25!10K4 dL/g, aPSZ0.707; KPCLZ1.09!10K3 dL/g,
aPCLZ0.600 in the [h]ZKMa, a Mark–Houwink relation-
ship) [34]. A Bruker ARX 400 MHz spectrometer was used
for the 1H NMR measurements with CDCl3 as the solvent
and tetramethylsilane (TMS) as internal reference. The
thermogravimetric analysis (TGA) was performed on a TA
SDT 2960 instrument at a heating rate of 10 8C/min in a
nitrogen atmosphere. DSC measurements were made on a
Thermal Analysis company Q-100 instrument with
Universal Analysis software under a dynamic atmosphere
of N2. The DSC cooling thermograms were obtained at a
rate of K10 8C/min from 200 to K90 8C, after the samples
were heated at 10 8C/min, and the melting thermograms of
all sample were obtained from the second heating run at
10 8C/min to 200 8C. The crystallinity of PCL Xc was
calculated from the heat of fusion DH (J/g) by XcZDH/
(DH0fw), where fw is the weight fraction of PCL block in
PCL-b-PMPCS and DH0 is heat of fusion for perfect PCL
crystals (DH0Z137.5 J/g) [30]. Transmission electron
microscopy (TEM) experiments were carried out on a
Hitachi H-800 electron microscopy. After the samples were
annealing at 150 8C, ultrathin sections were cut on a
cryoultramicrotome. The sections were stained using
RuO4 vapor at room temperature for 30 min. The regions
of PMPCS block and amorphous PCL block were
preferentially stained by RuO4 [30,38]. Polarized optical
microscopy (POM) observation was conducted on a Leitz
Laborlux 12 microscope with a Leitz 350 hot stage.
3. Results and discussion
3.1. Synthesis of macroinitiator
Ring-opening polymerization of CL in the presence of
Al(OiPr)3 in toluene was carried out at 0 8C according to the
other papers [39,40] (Scheme 1). Three different molecular
weight poly(3-caprolactones) (PCLs) were synthesized.
The GPC curves were symmetrically monomodal with
molecular weight distribution of 1.22–1.26. To get lower
polydispersity PCLs, PCLs were fractioned successfully.
 Y.-F. Zhao et al. / Polymer 46 (2005) 5396–5405 5399

Fig. 1. 1H NMR spectra of PCL113 (down) and macroinitiator PCL113-Br (up) (in CDCl3, 400 MHz).

PCL macroinitiators were prepared by end capping of living determined by means of 1H NMR spectroscopy are taken as
PCL with an excess of 2-bromo-2-methylpropionyl bromide actual molecular weights.
[35]. Fig. 1 shows the 1H NMR spectra of a typical PCL and
resulting PCL-Br macroinitiator with the tertiary halide end
3.2. Synthesis of PCL-b-PMPCS diblock copolymer
group. After reaction, the two methyl protons of the
2-bromoisobutyl moiety (k) appeared. From the relative
The macroinitiator (PCL-Br) was used to initiate MPCS
intensity of the peak (b) and the peak (c), the molecular weight
in chlorobenzene for synthesis of PCL-b-PMPCS block
of PCL was calculated. The degree of end functionalization
copolymer by ATRP with effective and cheap PMDETA
was obtained by comparison of the intensity of the peak (b) and
[42] (Scheme 2). Fig. 2 shows the GPC curves of a
the peak (k). The result showed that esterification was
macroinitiator PCL113-Br as well as a block copolymer
complete. The specifications of three macroinitiators are
presented in Table 1. The difference between molecular
weights obtained by GPC and those calculated from 1H NMR
is ascribed to the difference of hydrodynamic volume of PCL-
Br vs. polystyrene standards [41]. The molecular weights

Table 1
Molecular properties of PCL macroinitiators

Sample Mn!10K4 PDIa

GPCa NMRb Calcdc
PCL70-Br 1.58 0.80 0.78 1.08
PCL113-Br 2.26 1.29 1.14 1.11
PCL200-Br 3.50 2.28 1.82 1.10
a
Calibrated by PS standards.
b
Measured by 1H NMR.
c 1:067
Calculated according to the calibration equation: MPCL Z 0:258MPSt , Fig. 2. GPC curves of macroinitiator PCL113-Br and diblock copolymer
which is deduced from the Mark–Houwink relationship (Section 2). PCL113PMPCS103.
5400 Y.-F. Zhao et al. / Polymer 46 (2005) 5396–5405

Fig. 3. 1H NMR spectrum of PCL113PMPCS103 (in CDCl3, 400 MHz).

produced from it. It was found that the molecular weight of and PMPCS segment in copolymers vs. polystyrene
the copolymer increased and the GPC curve of the standards. The corresponding molecular weight distri-
copolymer was symmetrically single modal. This indicated butions were narrow throughout the polymerization
the high initiating efficient of initiator and a low degree of (PDI%1.11). We can conclude that the macromolecular
permanent termination by any side reaction. The successful initiator PCL-Br combined with CuBr, complexed by
preparation of PCL-b-PMPCS was proven by 1H NMR PMDETA induced a living polymerization of MPCS.
spectrum illustrated in Fig. 3. The composition in terms of
block weight fraction was calculated base on the ratio of the
3.4. Characterization and thermal behaviors of PCL-b-
peak (i) and peak (f). The spectrum was further used to
calculate the number molecular weight of diblock PMPCS
copolymer.
Table 2 summarized molecular characteristics of three
series of block copolymers with PCL blocks of 8000,
3.3. Kinetics of ATRP polymerization 12,900, and 22,800 molecular weights, respectively. For all
block copolymers, the final molecular weight distributions
ATRP of MPCS initiated by PCL-Br combined with are relatively narrow (PDI%1.11).
CuBr, complexed by PMDETA, was carried out in
chlorobenzene at 90 8C. To investigate the living character
of ATRP, a kinetic study was conducted with PCL113-Br as
macroinitiator. The polymerization condition was [PCL113-
Br]:[MPCS]:[CuBr]:[PMDETA]Z1:113:1:1 (in molar
ratios) at 40 wt% concentration. Fig. 4 shows the time
dependence of ln([M]0/[M]t) and the conversion. Each data
point represents a single experiment. The linear behavior of
ln([M]0/[M]t) was consistent with a controlled polymeriz-
ation that was first order in monomer concentration
indicating absence of termination. The plots of molecular
weight and polydispersity vs. conversion are illustrated in
Fig. 5. Both the Mn calculated from 1H NMR and that valued
by GPC were found to increase in direct proportion to the
monomer conversion. It must be noted that the Mn (GPC)
was lower than Mn (NMR) at low conversion, then higher Fig. 4. The relationships of the conversion and ln([M]0/[M]t) with the
than Mn (NMR) at high conversion. This may be caused by polymerization time for MPCS polymerization in chlorobenzene at 90 8C
the difference of the hydrodynamic volume of PCL segment using macroinitiator PCL113-Br.
 Y.-F. Zhao et al. / Polymer 46 (2005) 5396–5405 5401

Fig. 5. Dependence of molecular weight and PDI on the conversion for

MPCS polymerization in chlorobenzene at 90 8C using macroinitiator
PCL113-Br.
3.4.1. Thermal stability
The thermal stabilities of the diblock copolymers were
evaluated using thermogravimetric analysis (TGA). Perse-
naire et al. [43] have studied the thermal stability of PCL
prepared with the method as this work. Two-stage thermal
degradation mechanism has been proposed. The first stage
implies statistical rupture of PCL chains via pyrolysis
reaction. The second stage involves formation of 3-capro-
lactone as result of the unzipping degradation process. It
was also found that acetylation of hydroxyl end group can
Fig. 6. TGA curves obtained at heating rate of 10 8C/min under a nitrogen
atmosphere for PCL, PCL-Br, diblock copolymers and homo-PMPCS
prepared by ATRP (Mn,GPCZ20,600, PDIZ1.07).
limited the degradation by depolymerization. Fig. 6 shows
the weight loss curves for typical diblock copolymers with
PCL, PCL-Br and homo-PMPCS. It is not surprising that the
initial decomposition temperature of macroinitiator (PCL-
Br) improve obviously as compared with corresponding
precursor PCL. The temperatures at 5% weight loss for
selected samples are listed in Table 3. The results show that
the block copolymers have good thermal stabilities below
350 8C.

Table 2
Characterization data of molecular weight, polydispersities, and composition of three series of PCL and PCL-b-PMPCS

Sample Mn!10K4 PMPCSa PDIb Liquid

crystallinityc
GPCb NMRd Wt% Mol%
PCL70-Br 1.58 0.80 – – 1.08 –
PCL70PMPCS18 1.89 1.52 47.6 20.3 1.06 No
PCL70PMPCS44 2.33 2.59 69.0 38.6 1.06 Yes
PCL70PMPCS59 2.58 3.19 75.0 45.7 1.07 Yes
PCL70PMPCS103 3.22 4.97 83.9 59.5 1.07 Yes
PCL70PMPCS172 4.17 7.74 89.6 71.0 1.06 Yes
PCL113–Br 2.26 1.29 – – 1.11 –
PCL113PMPCS25 2.84 2.30 43.9 18.1 1.09 No
PCL113PMPCS46 2.99 3.13 58.9 28.8 1.09 Yes
PCL113PMPCS59 3.25 3.68 64.8 34.3 1.09 Yes
PCL113PMPCS103 4.07 5.45 76.3 47.7 1.08 Yes
PCL113PMPCS166 4.99 7.98 83.8 59.4 1.08 Yes
PCL113PMPCS226 5.83 10.41 87.6 66.6 1.08 Yes
PCL200-Br 3.50 2.28 – – 1.10 –
PCL200PMPCS16 3.91 2.93 22.1 7.6 1.09 No
PCL200PMPCS62 4.16 4.77 52.2 23.5 1.10 Yes
PCL200PMPCS109 4.83 6.68 66.0 35.3 1.08 Yes
PCL200PMPCS143 4.98 8.06 71.7 41.7 1.10 Yes
PCL200PMPCS155 5.70 8.57 73.4 43.7 1.09 Yes
PMPCSe 2.06 – – – 1.07 Yes
a
Determined from the Mn(PCL-Br) and Mn(PCL-b-PMPCS) by 1H NMR analysis.
b
Determined from GPC, calibrated by PS standards.
c
Examined by POM.
d
Calculated based on 1H NMR analysis of the PCL-Br and PCL-b-PMPCS.
e
Prepared by ATRP for comparison.
5402 Y.-F. Zhao et al. / Polymer 46 (2005) 5396–5405

Table 3
Thermal data from TGA and DSC measurements for homopolymers and diblock copolymersa

Sample Td (8C)b Tg,PCL (8C) Tm,PCL (8C) Xc (%) Tg,PMPCS (8C)

PCL70-Br 329.7 K59.3 55.2 58.9 –
PCL70PMPCS18 348.6 K55.7 51.6 37.6 –
PCL70PMPCS44 – K59.7 37.7 0.8 79.1
PCL70PMPCS59 365.9 K63.3 40.7 7.7 110.2
PCL70PMPCS103 – K62.1 40.5 8.4 117.4
PCL70PMPCS172 379.2 K64.2 42.8 10.9 120.6
PCL113-Br 368.2 K61.2 55.2 57.3 –
PCL113PMPCS25 363.9 – 52.8 44.2 –
PCL113PMPCS46 – – 51.9 46.9 97.9
PCL113PMPCS59 367.3 – 51.9 49.9 113.8
PCL113PMPCS103 – – 50.4 43.3 117.6
PCL113PMPCS166 378.8 – 48.9 37.2 118.4
PCL113PMPCS226 – – 47.0 32.6 120.0
PCL200–Br 368.0 K63.7 55.2 57.8 –
PCL200PMPCS16 368.0 K57.8 55.3 49.6 –
PCL200PMPCS62 – K59.5 55.6 49.5 110.9
PCL200PMPCS109 371.4 K59.8 53.9 47.3 117.2
PCL200PMPCS143 – K61.5 53.9 43.8 118.5
PCL200PMPCS155 376.3 K62.8 53.3 41.9 117.8
PMPCS 387.1 – – – 120.7
a
Data of DSC are determined from the second heating rate of 10 8C/min after cooling at 10 8C/min.
b
Temperature at 5% weight loss, determined from the TGA at heating rate of 10 8C/min under atmosphere of N2.

3.4.2. Liquid crystalline behavior showed a melting endotherm of the PCL block between 55
PMPCS is known to be nematic liquid crystalline and 53 8C and crystallinity was changed modestly from 50
polymer above its Tg and no clearing point is detected to 42%. This indicated that the crystallization of PCL block
until decomposition. The liquid crystalline behavior of the was affected by PMPCS block but the effect was not very
diblock copolymers was investigated by POM. As shown in pronounced.
Table 2, when DP of PMPCS segment is not less than 44, the Similar to the diblock copolymer based on PCL200-Br,
block copolymer exhibits liquid crystallinity. No relation- broadening Tg of PCL was observed for the PCL113-Br
ship between the liquid crystallinity and length of the PCL diblock copolymer with DP of PMPCS lower than 103.
block was found in three series of diblock copolymers. Chen Representative DSC curve is shown in Fig. 9. When the DP
et al. have studied the liquid crystalline behavior of different of the PMPCS increased (over 103), the Tg of PCL was
molecular weights PMPCS [23]. Based on Flory’s esti- puzzling due to low content as well as the high crystallinity
mation, the critical DP of 39–42 for stabilizing the LC phase of PCL. The experiment in order to prevent the PCL from
was calculated. The value is corresponding to our result of crystallization was failed by quenching PCL113PMPCS226
44. Representative LC texture of block copolymer is shown to K90 8C and equilibrated for 2 min. It was found that the
in Fig. 7. crystallization was not depressed. As a result, Tg of PCL
block was not shown clearly in the subsequently heating
3.4.3. Solid state behavior curve. However, Tgs of PMPCS block were clearly observed
When the question of immiscibility of diblock copoly-
mers is addressed, it is usually to measure the glass
transitions or melting points of each component [44,45].
At first, the diblock copolymers with longer length PCL
were investigated. Fig. 8 presents the typical thermograms
of diblock copolymer based on the PCL200-Br including
PCL200-Br and homo-PMPCS at second heating run. As
shown in Fig. 8, Tg of PCL was detected unambiguously for
this block copolymer like PCL homopolymer. A similar
trend was observed for copolymers based on PCL200-Br.
The values of transitions and crystallinities are summarized
in Table 3. When the DP of PMPCS was over 16, the Tg of
the PMPCS block was observed. These features demon-
strated the multiphase of block copolymers. With an
increasing of the PMPCS block, the block copolymer Fig. 7. LC texture of PCL70PMPCS44 at 200 8C.
 Y.-F. Zhao et al. / Polymer 46 (2005) 5396–5405
Fig. 8. DSC curves of PCL200-Br and diblock copolymer based on PCL200-Br at heating rate of 10 8C/min under a nitrogen atmosphere. The DSC curve of a LC
PMPCS prepared by ATRP is included for comparison (Mn,GPCZ20,600, PDIZ1.07).
for all block copolymers with the exception of PCL113-
PMPCS25 which had low DP of PMPCS (Table 3). This
demonstrated that the block copolymers remained micro-
phase separations. With an increase of content of the
PMPCS, the crystallization and melting temperature of PCL
block decreased. This indicated that the PMPCS block had
obviously effect on the crystallinity of PCL block.
The diblock copolymers based on PCL70-Br exhibited
thermal behavior significantly different from the other two
series of diblock copolymers. Fig. 10 presents the thermo-
gram of PCL70PMPCS59. The Tgs of PMPCS block were
clearly observed for copolymers which had higher DP of
PMPCS (over 18). The Tgs of PCL block for all copolymers
were observed even the content of PCL were lower than
10 wt%. This may due to lower crystallinity of PCL block.
As shown in Table 3, the crystallinities of diblock
copolymers were depressed notably and affected by content
of PMPCS strongly. In agreement with the literature
[46,47], the intensity and position of glass transition of the
PCL depend on the crystallinity of the PCL.
A detailed consideration of the data given in Table 3
showed that the diblock copolymer displayed a lower Tg and
the wider Tg range of PMPCS with the decrease of PMPCS
Fig. 9. Representative DSC curve of PCL113PMPCS103 at heating rate of
10 8C/min.
5403
length. The lower Tg of PMPCS was not caused by the
molecular weight of PMPCS block because previously
result showed that the Tg would not vary when Mn up to
1.0!104 [27]. This probably resulted from the partial
miscibility of the short length PMPCS and PCL blocks
above the melting temperature of PCL as a consequence of
the direct chemical interlinkage between the two com-
ponents. This interpretation would be consistent with higher
Tg of PCL block in block copolymer with low DP of PMPCS
(less than 44). Miscible and partially miscible block
copolymers were found in polystyrene-b-poly(3-caprolac-
tone) copolymer system when the molecular weight of
polystyrene was short (MnZ6000) [47]. Considering multi-
phase structure which was identified for diblock copolymer
with short length PCL (PCL70 series) in our work, it was
more appropriate to say that both the lower Tg of PMPCS
and the wider Tg range may be the result of size and
interface effects of the PMPCS layers being located between
molten PCL layers [12,47].
Though the main thermal transitions exhibited by PCL-b-
PMPCS block copolymers unambiguously concluded to
their multiphase character, this structural feature would be
further confirmed by the direct observation of the phase
morphology by TEM [48,49].
Fig. 10. DSC curve of PCL70PMPCS59 at heating rate of 10 8C/min.
5404 Y.-F. Zhao et al. / Polymer 46 (2005) 5396–5405

and directly observed through TEM. With a decrease of

PMPCS length in diblock copolymer, the partial miscibility
is proposed due to chemical interlinkage of short length
PCL and PMPCS. Crystallinity of PCL is greatly affected by
the length of the PCL block and composition of PMPCS in
copolymer. The liquid crystallinity is investigated by POM.
The result shows that the PMPCS block exhibit liquid
crystalline behavior when the DP of PMPCS is higher than
44. The length of PCL block has no remarkable effect on the
liquid crystallinity of PMPCS block. The fact that these
block copolymers contain crystallizable and liquid crystal-
line blocks, i.e. PCL and PMPCS, made them very
interesting from a structural point of view.

Acknowledgements

We gratefully acknowledge the financial support from

the National Natural Science Foundation of China (grant
20134010) and the Science Research Fund of the Chinese
Ministry of Education (grant 01001, 104005).

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